Plastic or coating composition



Patented Jan. 3, 1933 UNITED, STATES PATENT OFFICE ALP HONS O.' JAEGER,OF GRAFTON, PENNSYLVANIA, ASSIGNOR TO THE SELDEN COMPANY, OF PITTSBURGH,PENNSYLVANIA, A CORPORATION'OF DELAWARE PLASTIC OR COATING COMPOSITIONNo Drawing. Original application filed May 29, 1928, Serial No. 281,593.Divided and this application filed April 6, 1929.

and coating compositions, notably those containing ethers or esters ofcellulose, artificial 1o resins of the thermoplastic type, for examplephenol-aldehyde resins and phenol-ketone' resins, such as bakelite,phenol-furfural resins, aldehyde-urea resins, polybasic acidpolyhydricalcohol resins of the glycerol phthalate type and other compositionssuch as polymerlzation products of cumarone and indene, styrol, itaconicacid, and the like, together with sulfur resins,'resins prepared fromaromatic amines, casein plastics and the like. Many of these productshave been unsatisfactory because in the case of some plasticcompositions the resultant product is brittle or lacks flexibility ormachining qualities and in the case of coating compositions which aredissolved in solvents the complete evaporation of the solvents leavesfilms which are brittle and tend'to crack or peel. A class of com oundscalled softeners have been used to viate this, among the most importantsofteners being high boiling esters, such as those of phthalic acid,certain high boiling organic com ounds, such as various aromaticsulphonami es, and the like. Some of these products. are verysatisfactory but many have not achieved great commercial success becauseof excessive costs. Plastic and coating compositions using naturalresins, such as shellac and the like have also been plasticized.

The present invention relates to plastic compositions and compositionsfor forming coatings in which a new class of compounds are used assofteners, namely, the substituted phthalids. The substituted phthalids45 include thehydrogenated phthalids such as the tetraand particularlythe hexahydrophthalid, and the phthalids in which the oxymethyl group issubstituted by one or more .alkyl, 9. l, aralkyl or alkylidene radicals.v These re. icals in which the oxymethyl group Serial No. 353,268.

contains a substituent may also be hydrogenated.

The compounds with the exception of a few of the alkylidene compoundsare substantially inert, soluble in most of the solvents used and can bereadily incorporated with plastic compositions or coating compositions.They do not evaporate at the'temper'atures necessary for molding andendow the final product with the desired plasticity and workability. Theparticular substance to be used will depend to a certain extent on thenature of the plastic or coating compositions desired. Thus, where veryfluid compositions are desired the hydrogenated phthalids areparticularly suitable. For example, hexahydrophthalid is a colorless,odorless, heavy oil having a boiling point of 134138 'C. at 25 pressureand can be used in many plastic compositions and particularly coatingcompositions, such as for example, cellulose ester or ether lacquers,glycerol phthalate lacquers, and the like.

Hydrogenated phthalids may be produced by catalytic vapor phasehydrogenation of phthalic anhydride in the presence of suitablecatalysts or liquid phase hydrogenation of phthalic anhydride atordinary or superatmospheric, pressure, and it is sometimes desirable toproduce mixtures of phthalids and their hydrogenated products ormixtures of phthalid substance. The phthalids which are internal estersof orthoox-ymethylbenzoic acid or its derivatives vary in their physicalproperties depending on the degree of hydrogenation but they all possessthe desirable softening properties, are non-corrosive, relativelynon-volatile and satisfactorily withstand the temperatures required inmolding plastics.

Where less fluid condensation products are. desired the substitutedphthalids in which the oxymethyl group is substituted are desirable.

. fective plasticizers.

R CHR 04R C=R (Ix 040 040 040 monoalkylphthallds dialkylphthalldsalkylldenephthallds aryl OH-aryl C\m'yl 0:0 C=0 monoarylphthalidsdlarylphthullds The substituted ditetraand hexahydrophthalids are alsousuable, and constitute ef- A few substituted phthalids are themonoethylpropylbutyland isobutylphthalids, and hydrogenated phthalidspossessing in general these products are low melting solids or oils witha pleasant celery odor. Alkylidenephthalids, such as ethylidene andpropylidenephthalids, and the like, are of importance in certain phenolresins, and it seems probable that a certain amount of resinifyingreaction takes place between the alkylidene double bond and the phenol,since this double bond is of course of aldehydic character. It isobviously impossible to definitely determine just what takes place in aplastic composition which forms an infusible, insoluble end product.Examples of dialkylphthalids and hydrogenated phthalids are the diethyl,dipro yl, dibutyl and diisobutylphthalids and hydrogenated phthalids.Arylphthalids such as phenylphthalids or diphenylphthalids are also veryimportant, especially where extremely high boiling, normally solidplasticizers are desired, as in the case of some molding compositions.

The whole group of phthalid substances is characterized by softness andplasticity, relatively low vapor pressure and desirable resistance tohigh temperatures. Many of the 'products are colorless solids or oils,either odorless or possessing an agreeable odor, such as themonoalkylpht alids; some are colored, being yellow, yellow brown or redbrown oils or solids. All of the members are non-corrosive and do notevolve poisonous vapors, and possess very advantageous properties foruse as lasticizers.

t should be understood that the effect of the phthalids as plasticizersis primarily hysical. There is every reason to believe om their behaviorthat usually no chemical compounds are formed between the phthalids andthe plastic compositions in which they are used although of course thiscannot be determined with complete accuracy in every case as the finalproducts obtained for molding compositions are not of a character whichpermit of ready chemical analysis. V

eaaraa The following examples will illustrate the application of theinvention to a few of the immense number of plastic compositions andcoatin compositions which are of importance in industry today. It isunderstood that the invention is not limited to the details set forth inthese specific examples which are merely illustrations of a few typicalembodiments.

E mample 1 85 parts of glycerol phthalate resin, preferably freshlyprepared and fairly hard but not infusible, are mixed with 15 parts of asubstituted phthalid and heated to 150 C. accompanied by stirrin until ahomogeneous mixture is obtained. f desired, fillers may be incorporatedand the product can be molded preferably under pressure, preferably at150250 C., to form an infusible product. Heating at a lower temperature,such as 80150 C., can also be carried out at a lower pressure but alonger time is necessary.

Example 2 Phenol and formaldehyde are combined by well known methods toform a condensation product which can be rendered infusible by heating.The condensation is preferably carried out in the absence of fixedalkalis, water is removed, and 10-20% of monoethyl phthalid, orethylidene phthalid is homogeneously incorporated with the condensationproduct, heat being used, if necessary, to render the formersufficiently fluid to permit thorough mixture. The plasticizedcondensation product may be mixed with fillers, if necessary, such asasbestos, wood flour, kieselguhr and the like, and can then be hotmolded to set to an infusible product.

E mample 3 A fluid condensation product of phenol and formaldehyde isprepared and about 20-25% of hexahydrophthalid is homogeneouslyincorporated. This product can be used as an enamel or coating, ifnecessary with the addition of colors, and spreads well while hot on aclean metal surface. baked for a short time to harden the resin,pressure being applied if necessary. The enamel produced is superior tothose prepared from unplasticized phenol and formaldehyde condensationproducts, and is much more flexible. Its spreading and covering powersare also improved.

Example 4 A fusible phenol furfural condensation product is prepared inthe usual manner and after removing water and any free alkali which maybe present about 12% of a mixture of about 90% phthalid and 10% hydro-It should then be genated phthalids is incorporated, the condensationproduct being sufliciently heated to permit thorough incorporation.Fillers may be added, 'if desired, and the composition then hardened inthe usual manner. I

E wample 5 E mample 6' A fusible resin prepared by polymerization orcondensation of styrol is homogeneously admixed with about 58%substituted 3 phthalid and is then hardened in theusual manner.

E wample '7 A resin prepared by condensation or poly- 5 merization ofitaconic acid is admixed with 549% of hexahydrophthalid, suflicient heatbeing used to permit thorough incorporation,

and the resin is then hardened in the usual manner.

i Emample 8 A nitro cellulose plastic is prepared with from 10-30% ofmonophenyl phthalid, suflicient heat and agitation being used to permitthorough incorporation. The composition can be readily molded andarticles made from it may be polished to give a lustrous surface.Example 9 A cellulosenitrate lacquer is prepared with 0 low boilingsolvents to which about 1015% of hexahydrophthalid has been added. Thelacquer spreads and brushes easily forming a very flexible, tough film.

5 Example 10 and when suitable solvents havebeen used a very smooth,flexible film is obtained.

i5 1 Ewaxmplell A shellac molding composition is prepared and a phthalidsubstance is added to the amount of about by weight of the shellac.

Thorough/incorporation is effected by means of heat together withstirring or kneading.

The composition then can be readily molded giving a fine surface andbeing readily workable.

The foregoing examples give a few representative illustrations showingthe use of phthalid substances in plastics and lacquers. The preciseformulae, for example of the cellulose ester lacquers, has not beengiven as the present invention is not primarily concerned withparticular formulae. It has been found that the phthalids andparticularly the hydrogenated phthalids are very effective, high boilingplasticizers for a wide range of lacquers, especially brush lacquers.The invention is not limited to the use of particular formulae. Insteadof cellulose ester plastics, of course the inventionmay also be appliedto cellulose ether lacquers or plastics.

This application isa division of my prior application, Serial No.281,593, filed May 29, 1928.

- -What is claimed as new is:

1. A plasticized composition comprising a cellulose plastic and at leastone hydrogenated phthalid.

2. A plasticized composition comprising a cellulose plastic and amixture of hydrogenated phthalids.

3. A plasticized composition comprising a cellulose ester plastic and ahydrogenated phthalid substance having the formula in which at least oneX equals H and the remaining Xs are H or H and Y is H H-alkyl, dialkyl,H-aryl, diaryl or alkylidine.

4. A plasticized composition comprising a in which at least one X equalsH and the remaining Xs are H or H and Y is H gI-alkyl, dialkyl, H-aryl,diaryl or alkyli- 6. A coating composition comprising a cellulosederivative capable of forming films, at least one volatile solventtherefor and at least one hydrogenated phthalid substance having theformula in which at least one X equals H and the remaining Xs are H or Hand. Y'is H H-alkyldialkyl, H-aryl, diaryl or alkylidine.

7. A coating composition comprising a oellulose ester capable of formingfilms, at least one volatile solvent therefor and at least onehydrogenated phthalid substance having the formula in which at least oneX equals H and the remaining Xs are H or H and Y is H H-alkyl, dialkyl,H-aryl, diaryl or alkylidine.

8. A coating com osition comprising a cellulose nitrate capa 1e offorming films, at least one volatile solvent therefor and at least onehydrogenated phthalid substance having the formula in which at least oneequals H and the remaining Xs are'H or H dine.

Signed at Pittsburgh, Pennsylvania, this 3rd day of April, 1929.

ALPHQNS O. JAEGER.

and Y is H H-alkyl, dialkyl, H-aryl, diaryl or alkyli-

